European Journal of Organic Chemistry

Cover image for Vol. 2015 Issue 29

Early View (Online Version of Record published before inclusion in an issue)

Editor: Haymo Ross, Deputy Editor: Susan Wilkinson

Impact Factor: 3.065

ISI Journal Citation Reports © Ranking: 2014: 13/57 (Chemistry Organic)

Online ISSN: 1099-0690

Associated Title(s): Advanced Synthesis & Catalysis, Asian Journal of Organic Chemistry


  1. 1 - 54
  1. Short Communications

    1. Macrocycles

      A Modular Synthesis of Multidentate S-, N- and O-Containing Meta- and Paracyclophanes

      Omer K. Rasheed, Patrick D. Bailey, Amy Lawrence, Peter Quayle and James Raftery

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejoc.201501058

      Thumbnail image of graphical abstract

      A modular approach to macrocyclic assembly has enabled the synthesis of a library of macrocycles possessing multiple donor sites where chirality was readily introduced from (S)-alanine. Key to this approach was the facile, regioselective, nucleophilic ring opening of aziridines by dithiols followed by macrocylisation under conditions of high dilution.

  2. Full Papers

    1. Pyrrole Synthesis

      Regioselective [1N+2C+2C] Assembly of Fully Decorated Pyrroles from Primary Amines, 1,2-Diaza-1,3-dienes, and 2,3-­Allenoates

      Francesca R. Perrulli, Gianfranco Favi, Lucia De Crescentini, Orazio A. Attanasi, Stefania Santeusanio and Fabio Mantellini

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejoc.201501017

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      A sequential multicomponent reaction with three different substrates reacting in a well-defined manner to form fully substituted pyrroles has been developed. The process involves a primary amine, which enables two sequential nucleophilic additions and promotes, via enamino carbocyclization, the pyrrole ring formation. Regioselective preparation of the multifunctionalized pyrroles was thus achieved.

    2. Fused Heterocycles

      Easy Access to 1H-Pyrrolo[3′,4′:5,6]pyrido[2,3-d]pyrimidine-2,4,6,8(3H,7H)-tetraone and Selectively N7-Substituted Analogues Through Key Synthons

      Aurélien Tourteau, Eric Merlet, Alexis Bontemps, Mathilde Leland, Philippe Helissey, Sylviane Giorgi-Renault and Stéphanie Desbène-Finck

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejoc.201500971

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      New key synthons, 4-formyl-3-hydroxy-2,5-dioxo-2,5-dihydro-1H-pyrrole and its N-substituted analogues, have been developed for easy and versatile syntheses of heterocyclic skeletons, such as unsubstituted pyrrolo[3′,4′:5,6]pyrido[2,3-d]pyrimidine-2,4,6,8-tetraone.

    3. Process Development

      Palladium- and Nickel-Catalyzed Synthesis of Sodium Acrylate from Ethylene, CO2, and Phenolate Bases: Optimization of the Catalytic System for a Potential Process

      Simone Manzini, Núria Huguet, Oliver Trapp and Thomas Schaub

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejoc.201501113

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      The carboxylation of ethylene with CO2 in the presence of phenolate bases to give sodium acrylate was improved to develop the basis for a continuous process concept. The homogeneous nickel- or palladium-catalyzed transformation does not require stoichiometric reductants, and appropriate solvents as well as bases were identified that are suitable for a first recycling protocol.

  3. Short Communications

    1. Multicomponent System

      Solvent-Free Ball-Milling Biginelli Reaction by Subcomponent Synthesis

      Prasit Kumar Sahoo, Anima Bose and Prasenjit Mal

      Article first published online: 8 OCT 2015 | DOI: 10.1002/ejoc.201501039

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      Under solvent-free ball-milling conditions, multicomponent Biginelli reactions for the synthesis of dihydropyrimidones were performed by subcomponent synthesis of reagents (aldehydes) and catalyst (H+) from Br+ oxidation of benzyl alcohols.

  4. Full Papers

    1. Computation of Reaction Mechanisms

      Computational Investigation of the 1,4-Rh Shift in the [(Ph2PCH2CH2PPh2)Rh]-Catalyzed Alkyne Arylation Reaction

      Eric Assen B. Kantchev, Feng Zhou, Surya R. Pangestu, Michael B. Sullivan and Haibin Su

      Article first published online: 6 OCT 2015 | DOI: 10.1002/ejoc.201501098

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      DFT computations for the arylation of 2-butyne with phenylboronic acid mediated by [(dppe)RhI] [dppe = 1,2-bis(diphenylphosphanyl)ethane] reveal that (1) carborhodation is fast; (2) the barriers of the 1,4-shift and hydrolysis are approximately equal; and (3) the 1,4-Rh shift product is ca. 5 kcal mol–1 more stable than the non-rearranged product, in good agreement with the experimental results.

  5. Short Communications

    1. Porphyrinoids

      Efficient Synthesis of β-Alkynylcorroles

      Manuela Stefanelli, Mario L. Naitana, Marco Chiarini, Sara Nardis, Antonella Ricci, Frank R. Fronczek, Claudio Lo Sterzo, Kevin M. Smith and Roberto Paolesse

      Article first published online: 2 OCT 2015 | DOI: 10.1002/ejoc.201501138

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      Regioselective dibromination of corrole and subsequent Stille cross-coupling allow the successful preparation of triarylcorroles functionalized at the β positions with alkynyl substituents. These derivatives represent a novel approach to modulate the macrocycle properties, opening the way for corrole-based molecular architectures featuring extensive π conjugation.

    2. Configuration Determination

      Determination of the Relative Configuration of β-Amino Acid Esters Based on Residual Dipolar Couplings

      Thomas Niklas, Christian Steinmetzger, Weiping Liu, Daniel Zell, Dietmar Stalke, Lutz Ackermann and Michael John

      Article first published online: 2 OCT 2015 | DOI: 10.1002/ejoc.201500941

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      Two synthetic β-amino acid esters comprising an indan motif were structurally characterized by residual dipolar couplings. We demonstrate that the stability of Q factors against structural noise substantially facilitates the verification process. The “correct” structures differ by a single methyl group, which leads to a remarkable conformational change.

  6. Full Papers

    1. Perfluoroalkylated Pyrroles

      One-Pot Metal-Free Cascade Synthesis of 2-(Perfluoroalkyl)pyrroles

      Xuechun Sun, Jing Han, Jie Chen, Hongmei Deng, Min Shao, Hui Zhang and Weiguo Cao

      Article first published online: 2 OCT 2015 | DOI: 10.1002/ejoc.201501010

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      An efficient synthesis of 2-(perfluoroalkyl)pyrroles that employs a sequential one-pot three-component reaction between substituted ω-bromoacetophenones, anilines, and methyl perfluoroalk-2-ynoates has been developed. This transition-metal-free cascade process provides a practical way to construct perfluoroalkylated pyrroles in moderate to good yields.

    2. Cross-Coupling

      Linear and V-Shaped Alkynyl-1,3,5-tri­azines

      Peisen Gao, Zhenhua Wang, Xiu Wang, Weiqiang Zhang and Ziwei Gao

      Article first published online: 2 OCT 2015 | DOI: 10.1002/ejoc.201500948

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      A protocol has been developed for the synthesis of alkynyl-1,3,5-triazines, especially unsymmetrical alkynyl-1,3,5-triazines with two different alkynyl groups on the triazine core. The Pd2(dba)3/1,10-phenanthroline catalyst system was used in a copper-free Sonogashira coupling reaction followed using a Pd/Ag bimetallic system for the subsequent alkynyl coupling step. dba = dibenzylideneacetone, 1,10-phen = 1,10-phenanthroline, DIPEA = N,N-diisopropylethylamine, and Tf = trifluoromethylsulfonyl.

    3. Solid-Phase Fluorination

      Solid-Supported Iodonium Salts for Fluorinations

      Richard Edwards, Wilke de Vries, Andrew D. Westwell, Stephen Daniels and Thomas Wirth

      Article first published online: 1 OCT 2015 | DOI: 10.1002/ejoc.201500992

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      The preparation of solid-supported iodonium salt precursors has been investigated and their utility in the synthesis of fluoroarenes has been established. The successful radiofluorination of a simple solid-supported precursor shows the suitability of the method for the production of useful PET synthons.

    4. Indolocarbazoles

      Synthetic Studies on Indolocarbazoles: A Facile Synthesis of Staurosporinone Analogues

      Potharaju Raju, Ganesan Gobi Rajeshwaran and Arasambattu K. Mohanakrishnan

      Article first published online: 1 OCT 2015 | DOI: 10.1002/ejoc.201500939

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      A facile synthesis of indolocarbazoles was achieved that involves thermal electrocyclization of 2,3-divinylindole followed by triethyl phosphite-mediated nitrene insertion as key the reactions. The total synthesis of staurosporine aglycons was achieved from commercially available 2-methylindole that involves multiple steps.

    5. Solid-Phase Peptide Synthesis

      Solid-Phase Total Synthesis of the Proposed Structure of Coibamide A and Its Derivative: Highly Methylated Cyclic Depsipeptides

      Ganesh A. Sable, Jaekwan Park, Hyunsik Kim, Soo-Jeong Lim, Soonmin Jang and Dongyeol Lim

      Article first published online: 1 OCT 2015 | DOI: 10.1002/ejoc.201500697

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      Solid-phase total synthesis of the proposed structure of coibamide A and O-desmethyl coibamide A has been accomplished. The synthetic samples were studied by 2D NMR spectroscopic analysis and by computational modeling.

    6. Nucleobase Synthesis

      Synthesis of 5-/8-Halogenated or Ethynylated Lipophilic Nucleobases as Potential Synthetic Intermediates for Supramolec­ular Chemistry

      Nerea Bilbao, Violeta Vázquez-González, M. Teresa Aranda and David González-Rodríguez

      Article first published online: 1 OCT 2015 | DOI: 10.1002/ejoc.201501026

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      A series of lipophilic nucleobases substituted at the 5- (pyrimidines) or 8-position (purines) with either a halogen atom or a terminal triple bond have been synthesized. These molecules comprise a useful collection of synthetic intermediates for the field of chemical self-assembly.

    7. Single-Molecule Magnets

      Iodinated Bis(phthalocyaninato)terbium(III) Complexes: Versatile Platforms for Functionalization of Single-Molecule Magnets through Sonogashira Reaction

      Federico Bertani, Nicola Cristiani, Matteo Mannini, Roberta Pinalli, Roberta Sessoli and Enrico Dalcanale

      Article first published online: 1 OCT 2015 | DOI: 10.1002/ejoc.201501015

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      Iodinated TbPc2 have been synthesized and their single-molecule magnetic behavior has been studied by measuring their magnetic susceptibility. Incorporation of iodine in the molecular structure of the complex has allowed further functionalization through Sonogashira reaction. In this way, a wide range of LnPc2 derivatives bearing different functionalities can be easily obtained.

    8. Annelated Phthalocyanines

      Synthesis and Photophysical, Electrochemical and Theoretical Study of Thi­azole-Annelated Phthalocyanines

      Mária Nečedová, Peter Magdolen, Veronika Novakova, Marek Cigáň, Silvia Vlčková, Pavol Zahradník and Andrea Fülöpová

      Article first published online: 1 OCT 2015 | DOI: 10.1002/ejoc.201500785

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      To elucidate the effect of annelation of thiazole rings onto the phthalocyanine macrocyclic system, the photophysical and photochemical properties of a series of regioisomers were investigated. The properties and behaviour of the derivatives were compared with their well-known phthalocyanine analogues. The observed characteristics were consistent with those predicted by DFT calculations.

    9. Fused Heterocycles

      Synthesis of Thieno[3,2-e][1,4]diazepin-2-ones: Application of an Uncatalysed Pictet–Spengler Reaction

      Séverine Denoyelle, Guillaume Tambutet, Nicolas Masurier, Ludovic T. Maillard, Jean Martinez and Vincent Lisowski

      Article first published online: 1 OCT 2015 | DOI: 10.1002/ejoc.201500943

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      A new synthetic approach that uses an uncatalysed Pictet–Spengler cyclization reaction has been developed to access [3,2-e]-type fused thienodiazepinones.

  7. Short Communications

    1. Fluorescent Assemblies

      A Fluorescent 1,5-Naphthalenedisulfonate Anion-Linked Cucurbit[6]uril Framework

      Li Liu, Yuhang Yao, Xuefang Zhang and Ce Hao

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejoc.201501127

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      A highly ordered 3D framework from 1,5-naphthalenedisulfonate (1,5-NDS) and cucurbit[6]uril (CB[6]) is synthesized, wherein the 1,5-NDS anions act as linkers to connect the CB[6] units together through C–H···O H-bonds. The fluorescence wavelength of the assembly structure is blueshifted relative to that of 1,5-NDS and the fluorescence intensity is decreased, which are ascribed to the formed H-bonds.

  8. Full Papers

    1. Sulfonyl Azides

      Reactions of Thioacetamide Derivatives with Sulfonyl Azides: An Approach to Active-Methylene N-Sulfonylacetamidines

      Lidia Dianova, Vera Berseneva, Tetyana Beryozkina, Ilya Efimov, Maria Kosterina, Oleg Eltsov, Wim Dehaen and Vasiliy Bakulev

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejoc.201500968

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      An efficient, solvent-free and base-free approach to active-methylene N-sulfonylacetamidines has been developed.

    2. Intramolecular Anionic Cyclization

      Synthesis of Naphthofurans by tBuOK-Catalyzed Intramolecular Anionic Cycloaddition of Unsymmetrical Bis-propargyl Ethers

      Tamíris B. Grimaldi, Davi F. Back and Gilson Zeni

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejoc.201500969

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      Naphthofurans have been synthesized by tBuOK-catalyzed intramolecular anionic cycloaddition of unsymmetrical bis-propargyl ethers. The cyclization proceeded cleanly and smoothly under mild conditions with a catalytic amount of tBuOK as base in THF at room temperature in 15 min. The method tolerates neutral, electron-donating and -withdrawing, and heteroaryl groups in any part of the substrates.

    3. Gated and Twisted Hosts

      On the Transfer of Chirality, Thermodynamic Stability, and Folding Characteristics of Stereoisomeric Gated Baskets

      Lei Hu, Shane Polen, Alex M. Hardin, Yaowalak Pratumyot, Christopher M. Hadad and Jovica D. Badjić

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejoc.201501071

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      We have obtained stereoisomeric and gated baskets comprising a P or M twisted cup and amidopyridine gates at the rim. The gates form a seam of intramolecular hydrogen bonds to occlude space. They also assume a unidirectional orientation, induced by the cup's shape. Chemical and thermal stimuli trigger the basket's unfolding, which could be used in the design of switchable sensors and catalysts.

    4. p-Type DSSCs

      D–A–A-Type Organic Dyes for NiO-Based Dye-Sensitized Solar Cells

      Fei Wu, Jianlin Liu, Xi Li, Qunliang Song, Min Wang, Cheng Zhong and Linna Zhu

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejoc.201501036

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      Three new D–A–A-type organic dyes for p-type dye-sensitized solar cells were synthesized. The electron-withdrawing 2,1,3-benzothiadiazole (BT) unit was used for the first time in such dyes as the π-bridge between the triphenylamine donor and different acceptors. W2 shows a power conversion efficiency of 0.166 %, with a short circuit current of 4.16 mA cm–2 and an open circuit voltage of 0.121 V.

  9. Short Communications

    1. Photoredox Catalysis

      Preparation of 6-Difluoromethylphosphonated Phenanthridines by Visible-Light-Driven Radical Cyclization of 2-Isocyanobiphenyls

      Shuang Wang, Wen-Liang Jia, Lin Wang and Qiang Liu

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejoc.201500988

      Thumbnail image of graphical abstract

      The difluoromethylphosphonation of phenanthridine is achieved through an isocyanide insertion reaction under visible-light irradiation. By using diethyl bromodifluoromethylphosphonate as a radical resource and tris[2-phenylpyridinato-C2,N]iridium(III) [fac-Ir(ppy)3] as a photocatalyst, a series of 2-isocyanobiphenyls are smoothly transformed into 6-difluoromethylphosphonated phenanthridines.

  10. Full Papers

    1. Amino Alcohols

      Synthesis of Alkynyl-Glycinols by Lewis Acid Catalyzed Propargylic Substitution of Bis-Imidates

      Jekaterina Sirotkina, Liene Grigorjeva and Aigars Jirgensons

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejoc.201500937

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      Racemic and enantioenriched alkynyl-glycinol derivatives can be synthesized by Lewis acid catalyzed cyclization reaction of bis-trichloroacetimidates into oxazolines.

    2. Antigen Mimetics

      Structural Insights into the Binding of Sugar Receptors (Lectins) to a Synthetic Tricyclic Tn Mimetic and Its Glycopeptide Version

      Ana Ardá, Rosa Bosco, Javier Sastre, F. Javier Cañada, Sabine André, Hans-Joachim Gabius, Barbara Richichi, Jesus Jiménez-Barbero and Cristina Nativi

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejoc.201500874

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      A mimetic of the tumor-associated Tn antigen (CD175) and its glycopeptide interacts differently with lectins from a plant, a snail, and human macrophages. The conformation of the mimetic and the lectins' binding site topology contribute to the variation. Extrapolations about ligand recognition should thus be considered carefully, even for lectins that share specificity for a given monosaccharide.

    3. Total Synthesis

      Total Synthesis and Structural Reassignment of the γ-Lactone Polyketide from Diaporthe sp. SXZ-19

      Jhillu S. Yadav, Palash Dutta, Bogonda Ganganna and Eedubilli Srinivas

      Article first published online: 30 SEP 2015 | DOI: 10.1002/ejoc.201500811

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      The first stereoselective synthesis of the proposed structure of the γ-lactone isolated from Diaporthe sp. SXZ-19 has been achieved. The convergent pathway utilized Brown's alkoxyallylboration reaction to form the four stereogenic centers and a cross-metathesis to afford the (E)-olefin moiety of the side chain. This synthesis led to revised structural assignment of the natural product.

    4. Homo-C-Nucleosides

      Synthesis of Homo-C-Nucleoside Phosphoramidites and Their Site-Specific Incorporation into Oligonucleotides

      Katharina Höfler, Tristan Zimmermann, Dilver Peña Fuentes, Christian Vogel and Chris Meier

      Article first published online: 29 SEP 2015 | DOI: 10.1002/ejoc.201500996

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      3′-Phosphoramidites of thienopyrimidine and benzodiazepine homo-C-nucleosides were prepared and site-specifically incorporated into DNA. These modified oligonucleotides were hybridized with different DNA and RNA strands in order to study their duplex characteristics in terms of their melting temperatures and circular dichroism spectra.

    5. Heterocyclic Chemistry

      SNAr versus Buchwald–Hartwig Amination/Amidation in the Imidazo[2,1-b][1,3,4]thiadiazole Series

      Chloé Copin, Stéphane Massip, Jean-Michel Léger, Christian Jarry, Frédéric Buron and Sylvain Routier

      Article first published online: 29 SEP 2015 | DOI: 10.1002/ejoc.201500977

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      An efficient and convenient method has been developed for the preparation of C-2 aminated imidazo[1,2-b][1,3,4]thiadiazole derivatives by using SNAr or Buchwald–Hartwig reactions. The process was highly compatible with various functional groups and afforded the final compounds in very good yields.

    6. Isoxazoline Synthesis

      Synthesis of Isoxazoline Derivatives Based on Nitrile Oxide Cycloaddition of Nitroso-Nitro-Enamine

      László András Kondacs, Mihály Viktor Pilipecz, Zoltán Mucsi, Barbara Balázs, Tamás Gáti, Miklós Nyerges, András Dancsó and Péter Nemes

      Article first published online: 29 SEP 2015 | DOI: 10.1002/ejoc.201500905

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      A new and stable nitroso-nitro-enamine reagent, providing a nitrile oxide 1,3-dipole, has been treated with dipolarophiles in the course of 1,3-dipolar cycloaddition reactions to give a large number of novel isoxazolyl-pyrrolines. The mechanism of the reactions has been studied by experimental and theoretical methods.

    7. Thiodiketopiperazines

      Synthesis of New Diketopiperazines, Thiolation to Thiodiketopiperazines, and Examination of Their ROS-Generating Properties

      Sabilla Zhong, Angela E. E. Wandler, Ute Schepers, Martin Nieger and Stefan Bräse

      Article first published online: 29 SEP 2015 | DOI: 10.1002/ejoc.201500900

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      A variety of novel symmetrical and unsymmetrical thiodiketopiperazines have been prepared by methyl dichlorophosphite assisted dimerization of free amino acids and by thiolation of the resulting cyclic dipeptides with elemental sulfur and NaHMDS. Some of the sulfur compounds showed interesting activity in the generation of reactive oxygen species in HeLa cells.

    8. Enol Esters

      Ruthenium-Catalyzed Atom-Economical Stereo- and Regioselective Synthesis of Long-Chain Fatty Acid Enol Esters

      Rajesh K. Jena and Manish Bhattacharjee

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejoc.201501046

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      The ruthenium complex [Ru(dppp)2(CH3CN)Cl][BPh4] catalyzes the reaction of long-chain fatty acids with terminal alkynes to afford Z-enol esters stereoselectively in moderate to high yields.

    9. Sigmatropic Rearrangement

      Ireland–Claisen Rearrangement of 6-Methylene-1,4-oxazepan-2-ones

      Gints Smits, Artis Kinens and Ronalds Zemribo

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejoc.201500918

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      The Ireland–Claisen rearrangement of 6-methylene-1,4-oxazepan-2-one-derived boron enolates proceeds through an unusual double-chelated transition state, and both experimental and DFT calculations fully support this hypothesis. The obtained 4-(E)-ethylidene prolines can be used in the total syntheses of a number of biologically important natural products; PMB = p-methoxybenzyl, OTf = triflate.

    10. Rotaxanes

      Multivalent Molecular Shuttles – Effect of Increasing the Number of Centers in Switchable Catalysts

      Celedonio M. Álvarez, Héctor Barbero and Daniel Miguel

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejoc.201500942

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      Three molecular shuttles based upon ammonium/triazolinium salt motifs with one, two, and three catalytic centers are prepared. Their organocatalysis of two Michale-type reactions shows that the catalysis process occurs if the amine is exposed, but this catalysis stops if the ammonium salt is covered by the crown ether.

    11. Redox-Neutral Reactions

      Concise Access to 1,2-Pyrrole-Annulated Benzazepines through a Brønsted Acid Catalyzed Redox-Neutral Domino Reaction

      Peng-Fei Wang, Ya-Ping Huang, Xiaoan Wen, Hongbin Sun and Qing-Long Xu

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejoc.201501006

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      The reactions of 2-arylpyrroles with 2-(pyrrolidin-1-yl)-, 2-(piperidin-1-yl)-, or 2-morpholinobenzaldehydes by a dehydration/1,5-hydride shift/cyclization sequence affords 1,2-pyrrole-annulated benzazepines in yields of 25–65 %.

  11. Microreviews

    1. Transaminases in Biotechnology

      You have full text access to this OnlineOpen article
      The Industrial Age of Biocatalytic Transamination

      Michael Fuchs, Judith E. Farnberger and Wolfgang Kroutil

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejoc.201500852

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      ω-Transaminase-catalyzed preparation of chiral amines has emerged as one of the most successful fields in biocatalysis over the past ten years. This review covers the development of the catalytic systems and points out the most important applications, especially with regard to industrial and commercial use of the technology.

  12. Full Papers

    1. Domino Reactions

      A Highly Efficient Copper(I)-Catalyzed Cascade Reaction of o-Alkenylphenyl Isothiocyanates with Isocyanides Leading to 5H-Benzo[d]imidazo[5,1-b][1,3]thiazines

      Wenyan Hao, Jian Huang, Shanshan Jie and Mingzhong Cai

      Article first published online: 23 SEP 2015 | DOI: 10.1002/ejoc.201500800

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      The tandem addition–cyclization reaction of (E)-3-(2-isothiocyanatophenyl)acrylates and (E)-3-(2-isothiocyanatophenyl)acrylonitriles with isocyanides is described. This method offers an expedient route for the synthesis of 5H-benzo[d]imidazo[5,1-b][1,3]thiazines in good to excellent yields. The reaction involves [3+2] cycloaddition and subsequent intramolecular C–S bond formation.

  13. Short Communications

    1. Amino Acid Discrimination

      A Simple System Based on a Thiourea-Modified Fluorescein for ω-Amino Acid Discrimination

      Almudena Martí, Ana M. Costero, Pablo Gaviña and Margarita Parra

      Article first published online: 22 SEP 2015 | DOI: 10.1002/ejoc.201500991

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      A thiourea-modified fluorescein derivative is synthesized by reaction of fluorescein isothiocyanate with 2-(2-aminoethoxy)ethan-1-ol. UV/Vis absorption and fluorescence emission spectroscopy studies demonstrate that this heteroditopic receptor is able to discriminate among linear aliphatic ω-amino acids with different chain lengths.

  14. Full Papers

    1. Fluorinated Perylene Diimides

      Core Perylene Diimide Designs via Direct Bay- and ortho-(Poly)trifluoromethylation: Synthesis, Isolation, X-ray Structures, Optical and Electronic Properties

      Tyler T. Clikeman, Eric V. Bukovsky, Xue-Bin Wang, Yu-Sheng Chen, Garry Rumbles, Steven H. Strauss and Olga V. Boltalina

      Article first published online: 22 SEP 2015 | DOI: 10.1002/ejoc.201501024

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      Perylene dianhydrides and diimides with several CF3 groups were directly synthesized from solid PTCDA without halogenated precursors. Different compositions and isomers exhibit unique crystallographic packing arrangements. Gas-phase electron affinity and solution electrochemistry were compared with 143 electron-deficient perylene diimides.

    2. Alkoxyamines

      Investigation into the Chemistry of Highly Substituted [(Aminocyclopropyl)methyl]alk­oxyamines (3-Azabicyclo[3.1.0]hexanes)

      Stefan Hauck, Michael Kuepfert and Kai-Uwe Schoening

      Article first published online: 22 SEP 2015 | DOI: 10.1002/ejoc.201500693

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      The synthesis of bicyclic alkoxyamines is achieved by using a two-step reaction sequence. Enamines prepared from 1-alkoxy-4-(2,2′,6,6′-tetramethyl)piperidinones are first selectively chlorinated in the allyl position and then rearranged under the influence of various nucleophiles. The reaction has a broad substrate scope and gives access to highly substituted [(aminocyclopropyl)methyl]alkoxyamines.

    3. Asymmetric Allylic Alkylation

      Synthesis of a 4-Vinyltetrahydrocarbazole by Palladium-Catalyzed Asymmetric Allylic Alkylation of Indole-Containing Allylic Carbonates

      Luca Pignataro, Daniele Fiorito, Vito Vece, Raffaella Ferraccioli and Cesare Gennari

      Article first published online: 18 SEP 2015 | DOI: 10.1002/ejoc.201500979

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      A 4-vinyltetrahydrocarbazole is synthesized by Pd-catalyzed asymmetric allylic alkylation. Indole-containing allylic carbonates are cyclized with the aid of a chiral catalyst formed in situ from Pd(OAc)2 and members of the PhthalaPhos ligand library. With the best ligand, the product is obtained in up to 75 % ee with the R or S configuration depending on the geometry of the substrate's double bond.

  15. Short Communications

    1. C-H Activation

      Rhodium-Catalyzed Sequential Dehydrogenation/Deoxygenation in One-Pot: Efficient Synthesis of Dibenzothiophene Derivatives from Diaryl Sulfoxides

      Qiufeng Huang, Shurong Fu, Shaojia Ke, Hanbing Xiao, Xiaofeng Zhang and Shen Lin

      Article first published online: 18 SEP 2015 | DOI: 10.1002/ejoc.201501075

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      A novel strategy for the synthesis of dibenzothiophene derivatives was established through a one-pot intramolecular cross-dehydrogenative-coupling reaction of diaryl sulfoxides followed by deoxygenation with a Rh/Ag catalytic system.

    2. Carbocation Catalysis

      Carbocation Catalysis: Oxa-Diels–Alder Reactions of Unactivated Aldehydes and Simple Dienes

      Mahmoud Abd El Aleem Ali Ali El Remaily, Veluru Ramesh Naidu, Shengjun Ni and Johan Franzén

      Article first published online: 18 SEP 2015 | DOI: 10.1002/ejoc.201501112

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      Positive outcome: The trityl cation (TrBF4) is a highly efficient Lewis acid organocatalyst for the oxa-Diels–Alder reaction of various unactivated aromatic and aliphatic aldehydes and simple unactivated dienes, such as isoprene and 2,3-dimethylbutadiene, to give 3,6-dihydropyrane adducts in excellent to moderate yields with catalyst loadings down to 1.0 mol-%.

    3. Cyanating Reagents

      A Sterically Congested α-Cyanoamine as a Cyanating Reagent: Cyanation of Acetals and Orthoesters

      Shunsuke Kotani, Midori Sakamoto, Kazuki Osakama and Makoto Nakajima

      Article first published online: 16 SEP 2015 | DOI: 10.1002/ejoc.201501084

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      Sterically hindered α-cyanoamine is an effective cyanide source that mediates the cyanation of acetals and orthoesters in excellent yields. 1H NMR spectroscopy experiments reveal that trichlorosilyl triflate (SiCl3OTf) produces an intermediate, oxocarbenium cation species.

  16. Full Papers

    1. Fluorinated Amines

      Aza-Henry Reaction with CF3-Ketimines: An Efficient Approach to Trifluoromethylated β-Nitroamines, 1,2-Diamines, α-­Aminooximes, and Imidazolidinones

      Irina V. Kutovaya, Olga I. Shmatova, Viktor M. Tkachuk, Nina V. Melnichenko, Mikhail V. Vovk and Valentine G. Nenajdenko

      Article first published online: 16 SEP 2015 | DOI: 10.1002/ejoc.201500898

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      The aza-Henry reaction is an easy method for carbon–carbon bond formation that results in synthetically attractive nitroamines. The use of CF3-substituted ketimines can give access to fluorinated vicinal diamines, aminooximes, and imidazoline-2-ones.

    2. Antioxidant Polyphenols

      Conjugation of Hydroxytyrosol with Other Natural Phenolic Fragments: From Waste to Antioxidants and Antitumour Compounds

      Erika Tassano, Angela Alama, Andrea Basso, Giancarlo Dondo, Andrea Galatini, Renata Riva and Luca Banfi

      Article first published online: 16 SEP 2015 | DOI: 10.1002/ejoc.201500931

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      Hydroxytyrosol, a natural polyphenol, is converted into a series of analogues by conjugation with other naturally derived (poly)phenolic fragments, stressing step economy and operational simplicity. Ether and triazole linkers are used. Some of these substances have already been tested in radical scavenging and cytotoxicity assays.

    3. Thermal Rearrangements

      Investigations of the Thermal Responsiveness of 1,4,2-Oxathiazoles

      Russell J. Hewitt, Michelle Jui Hsien Ong, Yi Wee Lim and Brendan A. Burkett

      Article first published online: 14 SEP 2015 | DOI: 10.1002/ejoc.201500909

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      The first systematic study of the thermal rearrangement/fragmentation of 5,5-disubstituted 1,4,2-oxathiazoles into isothiocyanates is reported. Structure–activity relationships reveal that the choice of substituent at the 5-position of the 1,4,2-oxathiazoles not only influences the ease of fragmentation but may also have mechanistic consequences on the reaction.

  17. Short Communications

    1. Glycosylation

      Comparative Analysis of Fluorine-Directed Glycosylation Selectivity: Interrogating C2 [OH [RIGHTWARDS ARROW] F] Substitution in d-­Glucose and d-Galactose

      Nico Santschi and Ryan Gilmour

      Article first published online: 9 SEP 2015 | DOI: 10.1002/ejoc.201501081

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      The influence of C2 [OH [RIGHTWARDS ARROW] F] substitution on the stereochemical course of chemical glycosylation is interrogated in both D-glucose and its D-galactose. The differences in enthalpic and entropic contributions that discriminate these closely similar systems are extrapolated and are reconciled with a postulated induction model; (TCA = trichloroacetimidate).

  18. Full Papers

    1. Photochemistry

      Synthesis of Benzophenone Nucleosides and Their Photocatalytic Evaluation for [2+2] Cycloaddition in Aqueous Media

      Nadine Gaß and Hans-Achim Wagenknecht

      Article first published online: 9 SEP 2015 | DOI: 10.1002/ejoc.201500885

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      Bring it into water: Four benzophenone nucleosides that contain electron-donating substituents were prepared for use in a photocatalytic intramolecular [2+2] cycloaddition with a quinolone substrate in aqueous media. The Me-substituted benzophenone nucleoside was found to be the most efficient of the four examined catalysts.

    2. Addition–Rearrangement

      Enantioselective Installation of Quaternary Centers in Cyclic Oxonitriles

      Yakup Gunes, Nejat Arcelik, Ertan Sahin, Fraser F. Fleming and Ramazan Altundas

      Article first published online: 9 SEP 2015 | DOI: 10.1002/ejoc.201500895

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      This strategy allows the transfer of the stereogenic information of secondary allylic alcohols first to an alkoxyalkenenitrile intermediate, and then to a quaternary center through a Claisen rearrangement. This represents an easy method for the installation of a quaternary center in cyanocycloheptanones and bicycloalkenecarbonitriles in good yield and high selectivity, in a simple synthetic operation.

    3. Unnatural Amino Acids

      Enantioselective Synthesis of D-α-(Uracil-5-yl)glycine Derivatives and Their Racemization-Free Incorporation into a Model ­Peptide

      Nicole M. Weckenmann and Boris J. Nachtsheim

      Article first published online: 9 SEP 2015 | DOI: 10.1002/ejoc.201500914

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      A highly efficient enantioselective synthesis of three new α-(uracil-5-yl)amino acids from uracil using a dynamic kinetic resolution is presented. A study on the racemization-free incorporation of the Fmoc-protected amino acid into a model tripeptide is also described.

    4. Enals in Computational Chemistry

      In Silico Study on Chemical Properties and Reactivity of Enal Derivatives

      Gabriela L. Borosky and Kenneth K. Laali

      Article first published online: 9 SEP 2015 | DOI: 10.1002/ejoc.201500853

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      The chemical properties and reactivity of enals were studied by quantum-mechanical methods of calculation, by using protonation as model for enal activation, and by probing the formation and reactivity of anionic intermediates in the bis-silylated derivatives.

  19. Short Communications

    1. Practical Methods

      New Life for Diazoacetonitrile (N2CHCN): in situ Generation and Practical Synthesis of CN-Pyrazoles

      Pavel K. Mykhailiuk

      Article first published online: 4 SEP 2015 | DOI: 10.1002/ejoc.201501027

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      Explosive diazoacetonitrile (N2CHCN) is safely generated in situ and used in the practical synthesis of agrochemistry-related CN-pyrazoles. The developed method is expected to make this reagent very common in chemistry.

  20. Microreviews

    1. Green Chemistry

      Reactivity of Polar Organometallic Compounds in Unconventional Reaction Media: Challenges and Opportunities

      Joaquin García-Álvarez, Eva Hevia and Vito Capriati

      Article first published online: 2 SEP 2015 | DOI: 10.1002/ejoc.201500757

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      Stepping towards ideal polar organometallic processes! This microreview provides reliable evidence of the unstoppable transition of polar organometallic chemistry towards greener protocols, mainly represented by unconventional solvents. This contributes to make organometallic chemistry even more sustainable and prepares the ground for new, stimulating research.

    2. BODIPY Family Diversity

      Postfunctionalization of the BODIPY Core: Synthesis and Spectroscopy

      Noël Boens, Bram Verbelen and Wim Dehaen

      Article first published online: 18 AUG 2015 | DOI: 10.1002/ejoc.201500682

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      In this microreview, the various synthetic postmodification methodologies for functionalization of the BODIPY framework designed and developed by our research groups are comprehensively discussed, together with the electronic spectroscopic properties of the resulting dyes. With these new synthetic methodologies all the pyrrole C-ring positions and the meso-position can readily be substituted.


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